Exhaustion dyeing process with anthraquinone dyestuffs in water immiscible organic solvent

ABSTRACT

NEW ANTHRAQUINONE DYESTUFFS OF THE FORMULA   1-(H2N-),2-(HO-CH2-CH(-OH)-CH2-S-),4-X-ANTHRAQUINONE   IN WHICH X DENOTES A HYDROXYL, C1-C6-ALKYL-CARBONYLAMINO, C1-C6 - ALKYL - SULPHONYLAMINE, C1-C6-ALKOXY-CARBONYLAMINO, OPTIONALLY SUBSTITUTED ARYL-CARBONYLAMINO, ARYL-SULPHONYLAMINO, ARYLOXY-CARBONYLAMINO OR HETEROYLAMINO GROUP AND THEIR PREPARATION FROM CORRESPONDING 2HALOGEN-ANTHRAQUINONES. THEY ARE USED FOR DYEING SYNTHETIC FIBRE MATERIALS FROM ORGANIC SOLVENTS, ESPECIALLY FROM THOSE WHICH ARE IMMISCIBLE WITH WATER ACCORDING TO THE EXHAUSTION PROCESS.

United States Patent US. Cl. 8-39 12 Claims ABSTRACT OF THE DISCLOSURENew anthraquinone dyestuffs of the formula H I OH ll 0 X in which Xdenotes a hydroxyl, C -C -alkyl-carbonylamino, C -C alkylsulphonylamino, c -C -alkoxy-carbonylamino, optionally substitutedaryl-carbonylamino, aryl-sulphonylamino, aryloxy-earbonylamino orheteroylamino group and their preparation from corresponding 2-halogen-anthraquinones. They are used for dyeing synthetic fibrematerials from organic solvents, especially from those which areimmisicible with water, according to the exhaustion process.

This is a division of application Ser. No. 80,208, filed Oct. 12, 1970,now abandoned.

I The present invention relates to anthraquinone dyestuffs moreparticularly it concerns anthraquinone dyestuffs of the formula in whichX denotes a hydroxyl, C -C alkyl-carbonylamino, C -C alkylsulphonylamino, C C -alkoxy-carbonylamino, optionally substitutedaryl-carbonylamino, aryl-sulphonylamino, aryloxy-carbonylamino orheteroylamino group,

As the aryloxy-carbonylamino group: the phenoxyand4-nitrophenoxy-carbonylamino group; and

As the heteroylamino group: the a-fUI3I1C-, a-thiophene-, nicotine-,iso-nicotineand a-quinoline-carbonylamino group.

Representatives of the anthraquinone dyestuffs of formula I, accordingto the invention, are quoted in the examples.

The anthraquinone dyestuffs of formula I are prepared by the reaction ofanthraquinones of formula wherein X has the meaning given above and Haldenotes a chloro or bromo atom with thioglycerine, using solvents whichare inert under the reaction conditions such as pyridine,dimethylforrnamide or N-methyl-pyrrolidone, optionally in the presenceof an acid binding agent such as inorganic or organic bases.

The dyestuffs of formula (I) are excellently suited to the 'dyeing ofsynthetic fibre materials from organic solvents according to theexhaustion process, especially from such organic solvents as areimmiscible with water and of which the boiling points lie between 40 andC., for example aromatic hydrocarbons such as toluene and xylene, andhalogenated hydrocarbons, especially aliphatic chloro-hydrocarbons, suchas methylene chloride, chloroform, carbon tetrachloride,1,1-dichlorethane, 1,2- dichloroethane, 1,1,2 trichloroethane, 1,1,l,2tetrachlorethane, 1,1,2,2 tetrachloroethane, pentachlorethane, 1-chloropropane, 1,2-dichloropropane, 1,1,1,-trichloropropane,l-chlorobutane, 2-chlorobutane, 1,4dichlorobutane,1-chloro-2-methylpropane or Z-chloro-Z-methylpropane, as well asaliphatic fluoroor fluoro-chloro-hydrocarbons, such asperfluoro-n-hexane, 1,2,2-triflnorotrichlorethane and 1,1,1trifluoropentachloropropane, and aromatic chloroand fluorohydrocarbons,such as chlorobenzene, ,fiuorobenzene, chlorotoluene andbenzotrifiuoride. Tetrachlorethylene, trichlorethylene and1,1,1-trichlorethane have proved particularly suitable. Mixtures ofthese solvents can also be used.

It has frequently proved advantageous for the dyeing liquors to containsmall amounts, that is to say up to 1 percent by weight, preferably 0.5percent by weight, of water relative to the weight of the organicsolvents.

Furthermore, an addition of non-ionic auxiliary agents to the dyeingliquors has proved of value in some cases. Possible non-ionic auxiliaryagents are especially the known surface-active ethoxylation andpropoxylation products of fatty alcohols, alkylphenols, fatty acidamides and fatty acids as well as their mixtures; the auxiliary agentsare employed in an amount of 005-2 percent by weight relative to theweight of the organic solvent. Instead of adding the auxiliary agentsdirectly to the dyeing liquors, they can with advantage also be used forworking the dyestuffs into a dough and in this way be added to thedyeing liquors in the form of a dyestuff-auxiliary agent dough.

' The synthetic fibre materials to be dyed with the dyestuffs of formula(I) according to the invention are above all fibre materials ofpolyesters, for example polyethylene terephthalates orpolycyclohexanedimethylene terephthalate, of cellulose triacetate,cellulose 2 /z-acetate, polyacrylonitrile, synthetic polyamides, such ashexamethylenediamine adipate, poly-e-caprolactam or waminoundecane-acid,and polyurethanes. The fibre materials can be in the most diverseprocessing stages, for example in the form of filaments, flock, tops,yarn, piece goods, such as woven fabrics or knitted fabrics, or madeupgoods.

The dyeing according to the invention is preferably carried out inclosed apparatuses, for example by introducing the fibre materials intothe dyebath at room temperature, heating the dyebath to 6-0l70 C. andkeeping it at this temperature until the liquor is exhausted; this isgenerally the case after 10-60 minutes. After cooling to roomtemperature, the liquor is separated off and the fibre materials are,optionally after brief rinsing with fresh organic solvent, freed of theadhering solvent by suction treatment or centrifuging and subsequentdrying in a warm stream of air. With the aid of the process according tothe invention it is possible to dye synthetic fibre materials in asimple manner from organic solvents to give high dyestutf yields andexcellent fastness properties.

The dyestuffs according to the invention are largely insoluble in theorganic solvents which are immiscible with water. They are distinguishedfrom the dyestuffs hitherto used for dyeing synthetic fibre materialsfrom organic solvents by a significantly better affinity and anincreased fastness to sublimation. A further advantage of the dyestuffsaccording to the invention consists of the fact that the depth of colourof the resulting dyeings is, for a given dyestuif: goods to be dyedratio, largely independent of the concentration of the dyestutf in thedyeing liquor and hence also independent on the liquor ratio. Because ofthis independence of the liquor ratio employed, the dyestuffs accordingto the invention can be carried out in all known dyeing devices, such aswinch dyers, jiggers and the like, which are known each to work with adifferent liquor ratio, and yield reproducible dyemgs.

It should be pointed out that mixtures of the dyestuffs according to theinvention at times give a better colour yield than the individualdyestuffs.

The parts indicated in the examples which follow are parts by Weight,unless otherwise stated.

EXAMPLE 1 100 parts of a woven fabric of texturised polyethyleneterephthalate fibres are introduced at room temperature, without priorcleaning, into a dyebath which is prepared from 1 part of l-amino2-(2,3-dihydroxy-propylmcrcapto)-4-hydroxyanthraquinone and 1000 partsof tetrachlorethylene. The bath is heated to 115 C. over the course of10 minutes with vigorous circulation of the liquor and is kept at thistemperature for 30 minutes. The liquor is then separated olf and thegoods being dyed are rinsed with fresh solvent for 5 minutes at about 40C. After separating off the rinsing liquor, the goods being dyed arecentrifuged and dried in a stream of air. A strong ruby-red dyeinghaving excellent fastness to sublimation as well as very good fastnessto washing and rubbing is obtained.

An equivalent ruby-red dyeing was obtained in the same manner on a wovenfabric of polycyclohexane-dimethylene terephthalate fibres.

If the tetrachlorethylene is replaced by the same amount of1,1,2-trichloroethane, an equivalent dyeting is obtained.

The dyestuff used had been manufactured as follows: 32 parts ofl-amino-2-bromo-4-hydroxy-anthraquinone were dissolved in 150 parts ofpyridine, mixed with 7 parts of powdered potassium hydroxide and 20parts by volume of thioglycerine, and stirred for 3 hours at 45-50" C.After adding 180 parts of methanol and 10 parts of glacial acetic acid,the dyestulf which had separated out was filtered off and washed withmethanol and water. 32.5 parts of dyestutf were obtained melting at186-187 C. after recrystallisation from anisole.

.4 EXAMPLE 2 100 parts of a woven fabric of triacetate fibres areintroduced at room temperature into a dyebath which is prepared from 1part of l-amino-2(2,3-dihydroxy-propylmercapto) 4benzenesulphonamido-anthraquinone and 1000 parts of tetrachlorethylene.The bath is heated to 110 C. over the course of 20 minutes with vigorouscirculation of the liquor, and is kept at this temperature for 45minutes. The liquor is then separated off and the woven fabric is rinsedwith fresh tetrachlorethylene at 40 C. After separating off the rinsingliquor, the goods being dyed are freed of the adhering solvent bycentrifuging and drying in a stream of air. A full, ruby-red dyeing ofexcellent fastness properties is obtained.

If the 1000 parts of tetrachlorethylene are replaced by the same amountof 1,1,2-trichlorethane, l,l,l,2-tetrachlorethane,l,l,2,2-tetrachlorethane, pentachlorethane, 1,2-dichloropropane,2-chlorobutane, 1,4-dichlorobutane, chlorobenzene or chlorotoluene,equivalent dyeings were obtained.

The dyestulf used had been obtained as described in Example 1, exceptthat instead of the 32 parts of l-amino- 2-bromo-4-hydroxy-anthraquinonethe equivalent amount of I-amino-Z-bromo 4benzenesulphonamido-anthraquinone was used.

EXAMPLE 3 100 parts of yarn of acetate filaments are introduced at about22 C. into a dyebath which is prepared from 1 part of the dyestuff usedin Example 1, 1000 parts of tetrachlorethylene, 1.5 parts of oleic acidethanolamide, 1.5 parts of oleyl alcohol heptaethylene glycol ether and6 parts of water. The bath is warmed to 78 C. over the course of 20minutes and kept at this temperature for 45 minutes. After separating ohthe dyeing liquor and rinsing with fresh tetrachlorethylene, the goodsbeing dyed are freed of the adhering solvent by suction treatment anddrying in a stream of air. A brilliant ruby-red dyeing is obtained.

EXAMPLE 4 100 parts of polyacrylonitrile fibre yarn are dyed in a bathwhich is prepared as described in Example 3. The bath is warmed to 100C. over the course of 20 minutes and kept at this temperature for -30minutes. After the usual washing and drying, a ruby-red dyeing havinggood fastness properties is obtained.

EXAMPLE 5' 100 parts of fibre yarn of poly-e-eaprolactam are introducedat room temperature into a dyebath which contains 1 part ofl-amino-2-(2,3 dihydroxy-propylmercapto)-4- benzloylamioanthraquinone in1000 parts of tetrachlorethylene. The bath is warmed to 100 C. over thecourse of 20 minutes, with vigorous circulation of the liquor, and iskept at this temperature for 40 minutes. After this time, the liquor isseparated off, the goods are briefly rinsed with fresh solvent, andafter centrifuging the dyeing is dried in a stream of air. A ruby-reddyeing with good fastness properties is obtained.

An equivalent dyeing was also obtained on yarns of ipolyhexamethylenediamine adipate fibres.

The colour strength of the dyeing can be increased by adding 1 part ofoleic acid ethanolamide, 1 part of oleyl alcohol heptaethylene glycolether and 4 parts of water to the dyebath.

The dyestuff used had been obtained as described in Example 1, exceptthat instead of the 32 parts of lamino-2-bromo 4 hydroxy-anthraquinonethe equivalent amount of 1-amino-2-bromo 4 benzoylamino-anthraquinonewas used.

If instead of the dyestuff mentioned, the equivalent amount of one ofthe dyestuffs listed in the following Table was used, ruby-red dyeingswith equivalent fastness properties were obtained on woven fabrics ofpolyester,

triacetate, polyamide, cellulose 2 /z-acetate, polyacrylonitrile orpolyurethane fibres.

EXAMPLE 24 50 parts of polyethylene terephthalate filaments areintroduced into a. dyebath which is prepared from 0.5 parts of thedyestuff used in Example 2 and 0.5 parts of the dyestuif used in Example5, 1.5 parts of oleic acid ethanol-. amide, 1.5 parts of oleyl alcoholheptaethylene glycol ether, 6 parts of water and 500 parts oftetrachlorethylene. The bath is heated to 120 C. over the course of 10minutes, with vigorous circulation of the liquor, and is kept at thistemperature for 45 minutes. After separating off the dyeing liquor, thegoods being dyed are rinsed with fresh solvent at 40 C. and are dried ina stream of air after removing the rinsing liquor. A deep ruby-reddyeing of excellent fastness to washing and sublimation is obtained.

EXAMPLE 25 100 parts of polyethylene terephthalate woven fabric are dyedfor 30 minutes at 115 C. in a dyebath of 1 part of 1 amino2-(2,3-dihydroxy-propylmercapto)-4-ptosylamino-anthraquinone, 3 parts ofoleic acid ethanol amide, 3 parts of oleyl alcohol heptaethylene glycolether, 12 parts of water and 1600 parts of tetrachlorethylene. Afterrinsing with fresh tetrachlorethylene and drying, a strong ruby-reddyeing having very good fastness to sublimation, washing and rubbing isobtained.

The dy'estufi? used had been manufactured in the following manner: 30parts of l-amino-2-bromo-4-p-tosylaminoanthraquinone were dissolved in150 parts of N-methylpyrrolidone and mixed with 6 parts of potassiumhydroxide and 20 parts by volume of thioglycerine. The reaction mixturewas stirred for /2 hour at 30-40 C., cooled and mixed with 180 parts ofmethanol, 140 parts of water and 10 parts of glacial acetic acid.Thereafter the dyestuif was filtered off, washed and dried. Yield: 31.2parts; melting point, after recrystallisation from anisole: 169-170 C.

EXAMPLE 26 100 parts of a woven fabric of textured polyethyleneterephthalate fibres are introduced at room temperature, without priorcleaning, into a dyebath which is prepared from 1 part ofl-amino-2(2,3-dihydroxy-propylmercapto)-4-methanesulphenylamino-anthraquinoneand 1000 parts of tetrachlorethylene, and are dyed for 30 minutes at 115C. After the customary rinsing and drying, at rubyred dyeing having verygood fastness to sublimation, wash ing and rubbing is obtained.

The dyestuif used had been manufactured as follows: 15 parts of1-amino-2-bromo-4-me'thanesulphonamido-an thraquinone were dissolved inparts of pyridine and mixed with 3 parts of powdered potassium hydroxideand 12 parts by volume of thioglycerine. After stirring for one hour at30-35 C., the reaction mixture was briefly warmed to 60 C., again cooledand mixed with 140 parts of methanol, 3 parts of glacial acetic acid and30 parts of Water. The dyestuif which has crystallised out is filteredoff, washed and dried. 14.3 parts were obtained. Melting point, afterrecrystallisation from ethylene glycol monomethyl ether: 165-166 C.

EXAMPLE 27 parts of a woven fabric of triacetate fibres are introducedat room temperature into a dyebath which contains 1 part of1-amino-2-(2,3-dihydroxy-propylmercapto)-4-(4'-methoxy benzoylamino)anthraquinone in 1000 parts of tetrachlorethylene. The bath is warmed to100 C. over the course of 20 minutes, with vigorous circulation of theliquor, and is kept at this temperature for 40 minutes. After separatingoff the dying liquor, the goods, being dyed are briefly rinsed withfresh solvent and after centrifuging 01f the washing liquor are dried ina stream of air. A strong ruby-red dyeing having good fastnessproperties is obtained.

The dyestuif used had been obtained as described in Example 26, exceptthat instead of the 15 parts of 1-amino-2-bromo-4-methanesulphonamido-anthraquinone the equivalent amount ofl-amino-2-bromo-4-(4-methoxy-benzoylamino)-anthraquinone was used.

EXAMPLE 28 100 parts of a woven fabric of anionically modifiedpolyethylene terephthalate are dyed for 30 minutes at C. in a dyebath of1 part of the dyestulf described in Example 1, 3 parts of oleic acidethanolamide, 3 parts of oleyl alcohol heptaethylene glycol ether, 12parts of water and 1600 parts of tetrachlorethylene. After rinsing withfresh tetrachlorethylene and drying, at strong ruby-red dyeing havingvery good fastness to sublimation, washing and rubbing is obtained.

An equivalent dyeing was also obtained on a woven fabric of anionicallymodified polyhexamethylenediamine adipate.

What is claimed is:

1. A process of dyeing synthetic fiber material comprising the steps of(A) immersing a synthetic fiber material in a dyebath consistingessentially of water-immiscible organic solvent having a boiling pointof 40-l70 C. and an anthraquinone dyestuif of the formula 0 NHQ II I OHI A s onion-onion aryloxy-carbonylamino in .Which arylis phenyl- 01- 4nitrophenyl-; heteroylamino in which the heteroyl group is t-furane,fl-thiophene-, nicotine-, iso-nicotineor qqinoline-carbonyl. I a I 3.The process of Claim 1 in vwhich X is aryl-carbonylamino in which arylis phenyl-, methylpheny1-, diphenyl-, chlorophenyh, dichlorophenylw,methoxyphenyl-, nitrophenyl-, methylnitrophenyl-, wnaphthylorfi-naphthyl oraryl-sulphonylamino in which arylis phenyl-, methyl-.phenyl-, chloropheny-1-, dichlorophenyl-, .nitrophenylor naphthyl-.

4, The process of Claim 1 in which X is hydroxy. 5. The process of Claim1 in which X is C .C -alkyl-carbonylamino or C -C -alkyl-sulphonylamino.

6. The process of Claim 1 in which said Water-immiscible organic solventis an aliphatic chlorohydrocarbon.

7. The process of Claim 1 in which said dyebath contains up to 1% byweight of water relative to said water, immiscible organic solvent.

8. The process of Claim 1 in which said synthetic fiber material ispolyester, cellulose triacetate, cellulose 2 /2 acetate,polyacrylonitrile or polyamide.

- 9. The process of Claim 1 in which said synthetic fiber material ispolyester.

10. Theiprocessyqf Claim 1 in which said dyebath is water-free. I v t r11. The process of Claim 1 in which X is aryl-sulfonylamin'o and' aryl"i's phenylg methylph'enylchlorophenyl-, dichlorophenyl-, nitrophenylornaphthyl-. 4

12. The process-0f Claim 1 in which said dyebath con-' tains up to.1%byweight oftwater relativejto said waterimmiscible organic solvent. v

- References 1 UNITED STATES P TENTS 3,072,683 1/1963 'StraIey e861. i'2 6 0347.2 3,486,837, 12/1969 tNeeffet al.' 8--39 3,394,133 7/1968Stral'eyet a1. 2 0 -37);

FOREIGNPATENTS v r I 3 870,948 6/19 61;.v Gre at Britain 260 3711,192,984 5/1970 Great Britain 8-174 20 THOMAS J. HERBERT, J R.;-Primary Examiner

